KR100632001B1 - Glass compositions for low temperature sintering, glass frit, dielectric compositions and multilayer ceramic condenser using the same - Google Patents

Glass compositions for low temperature sintering, glass frit, dielectric compositions and multilayer ceramic condenser using the same Download PDF

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KR100632001B1
KR100632001B1 KR1020050069342A KR20050069342A KR100632001B1 KR 100632001 B1 KR100632001 B1 KR 100632001B1 KR 1020050069342 A KR1020050069342 A KR 1020050069342A KR 20050069342 A KR20050069342 A KR 20050069342A KR 100632001 B1 KR100632001 B1 KR 100632001B1
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glass
dielectric
mol
multilayer ceramic
composition
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김찬공
나은상
손성범
송태호
정한승
허강헌
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삼성전기주식회사
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    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089Glass compositions containing silica with 40% to 90% silica, by weight containing boron
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    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02Frit compositions, i.e. in a powdered or comminuted form
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Abstract

Provided are a glass composition, a glass frit, a dielectric composition, and a multilayer ceramic capacitor using the same as a sintering aid for low temperature sintering at 1100 ° C. or lower. The glass composition according to the present invention consists of aLi 2 O-bK 2 O-cCaO-dBaO-eB 2 O 3 -fSiO 2 , wherein a, b, c, d, e and f are a + b + c +. d + e + f = 100, 2 ≦ a ≦ 10, 2 ≦ b ≦ 10, 0 ≦ c ≦ 25, 0 ≦ d ≦ 25, 5 ≦ e ≦ 20 and 50 ≦ f ≦ 80.
Laminated Ceramic Capacitors, Dielectric Compositions, Glass Frit, Glass Compositions

Description

Glass Compositions, Low Temperature Sintering, Glass Frit, Dielectric Compositions and Multilayer Ceramic Condenser Using the Same

1 is a cross-sectional view of a multilayer ceramic capacitor according to an embodiment of the present invention.

2 is a process flowchart showing the manufacturing process of the multilayer ceramic capacitor according to the embodiment of the present invention.

<Description of the symbols for the main parts of the drawings>

100: multilayer ceramic capacitor 101, 103: internal electrode

102: dielectric layer 104, 105: external electrode

110: condenser body

The present invention relates to glass compositions, glass frits, dielectric compositions, and multilayer ceramic capacitors using the same. More particularly, the present invention relates to a borosilicate-based glass frit having a high specific surface area, excellent high temperature fluidity, excellent solubility in BaTiO 3 , a composition thereof, a dielectric composition containing the same, and a multilayer ceramic capacitor using the same.

Recently, as miniaturization, weight reduction, and high performance of electric and electronic products have been rapidly progressed, multilayer ceramic capacitors used therein are gradually becoming smaller and higher in capacity. For miniaturization and high capacity, the dielectric layers used for multilayer ceramic capacitors are becoming thinner and the number of layers of the dielectric layers is also increasing. Recently, a supercapacitor has been realized by stacking 470 or more BaTiO 3 dielectric layers having a thickness of 3 μm or less, and in some cases, a dielectric layer having a thickness of 2 μm or more is required. As such, the ultra-high volume and high lamination of the multilayer ceramic capacitor is inevitably required to thin the dielectric layer, and as the dielectric becomes thin, securing a uniform microstructure is the most important factor in realizing the dielectric properties and reliability of the capacitor.

In addition to the thinning of the dielectric layers, the connectivity of the internal electrodes is also a very important factor in the capacitance implementation of multilayer ceramic capacitors. In general, the Ni electrode layer used as the internal electrode is sintered at a temperature of several hundred ° C. lower than the sintering temperature of the ceramic dielectric. If the sintering temperature is too high, the inconsistency of the sintering shrinkage between the internal electrode layer and the dielectric layer is intensified. delamination is likely to occur. In addition, as the heat treatment (sintering) at a high temperature causes the electrode to break rapidly due to agglomeration of the Ni electrode layer, the capacity of the capacitor is lowered, and a short circuit generation rate (short rate) is increased. Therefore, in order to prevent this, it is preferable to sinter the Ni internal electrode and the ceramic dielectric layer in a reducing atmosphere at a low temperature of 1100 ° C or less.

In addition, in order for a multilayer ceramic capacitor to exhibit high quality performance, temperature stability of its capacity is required. Depending on the application of the capacitor, the X5R dielectric properties of the EIA standard are required, which requires that the rate of change (ΔC) of the capacity be within ± 15% at -55 ° C to 85 ° C (reference temperature 25 ° C).

As a conventional sintering aid for producing a multilayer ceramic capacitor, a BaO-CaO-SiO 2 -based glass frit or a BaSiO 3 -based mixed powder is usually used. However, these sintering aids have a high melting point of 1200 ° C or higher, and therefore, it is difficult to promote sintering at a low temperature of 1150 ° C or lower. In addition, in the case of using the conventional glassy sintering aid, there is a problem that the sintering temperature range for manufacturing a multilayer ceramic capacitor is very limited due to the rapid progress of liquid phase formation at a high temperature. Japanese Unexamined Patent Publication No. 2000-311828 discloses (Ba, Ca) x SiO 2 + x (x = 0.8 to 1.2) as a sintering aid for producing a multilayer ceramic capacitor. However, since the dielectric layer containing the sintering aid disclosed in the above publication has a sintering temperature of more than 1100 ° C, there is a limit in implementing a multilayer ceramic capacitor having an ultra-thin dielectric layer of 3 mu m or less.

The present invention has been made to solve the above problems, the object of which is to sinter the BaTiO 3 dielectric uniformly at a low temperature of 1100 ℃ or less and to satisfy the X5R dielectric properties and the glass composition for low temperature sintering To provide a frit.

Another object of the present invention is to provide a dielectric composition capable of sintering at a low temperature of 1100 ° C. or lower and satisfying X5R dielectric properties by using the glass composition.

It is still another object of the present invention to provide a multilayer ceramic capacitor that can be manufactured by low temperature sintering at 1100 ° C. or lower and exhibits X5R dielectric properties by using the dielectric composition.

In order to achieve the above technical problem, the glass composition according to the present invention is composed of aLi 2 O-bK 2 O-cCaO-dBaO-eB 2 O 3 -fSiO 2 , the a, b, c, d, e and f is a + b + c + d + e + f = 100, 2≤a≤10, 2≤b≤10, 0≤c≤25, 0≤d≤25, 5≤e≤20 and 50≤f≤ Meets 80

In the glass composition, preferably, the a, b, c, d, e and f is 3≤a≤8, 2≤b≤5, 0≤c≤15, 0≤d≤15, 10≤e It satisfies ≤20 and 55≤f≤75. More preferably, the a, b, c, d, e and f is 3≤a≤8, 2≤b≤5, 0≤c≤15, 5≤d≤15, 12.5≤e≤17.5, 60≤ f≤75 is satisfied.

The glass frit of the present invention has the composition formula aLi 2 O-bK 2 O-cCaO-dBaO-eB 2 O 3 -fSiO 2 (a + b + c + d + e + f = 100, 2 ≦ a ≦ 10, 2 ≦ b ≦ 10, 0 ≦ c ≦ 25, 0 ≦ d ≦ 25, 5 ≦ e ≦ 20, and 50 ≦ f ≦ 80), in the form of ultrafine spherical powder having a particle size of 100 to 300 nm. It is.

In the glass frit, preferably, the a, b, c, d, e and f are 3≤a≤8, 2≤b≤5, 0≤c≤15, 0≤d≤15, 10≤e It satisfies ≤20 and 55≤f≤75. More preferably, the a, b, c, d, e and f is 3≤a≤8, 2≤b≤5, 0≤c≤15, 5≤d≤15, 12.5≤e≤17.5, 60≤ f≤75 is satisfied.

In order to achieve another object of the present invention, the dielectric composition of the present invention,

BaTiO 3 which is a main component; A minor component containing the glass composition,

The auxiliary component is, relative to the main component as 100 mol, the glass composition of 1.0 to 3.0 mol, MgCO 3 0.5 ~ 2.0 mol, rare earth oxide (the rare earth oxide is Y 2 O 3, Ho 2 O 3, Dy 2 O 3 and Yb 2 Selected from the group consisting of O 3 ) 0.3-1.0 mol and 0.05-1.0 mol MnO.

In order to achieve another object of the present invention, the multilayer ceramic capacitor of the present invention includes a plurality of dielectric layers, internal electrodes formed between the dielectric layers, and external electrodes electrically connected to the internal electrodes, wherein the dielectric layers are described above. It consists of a dielectric composition according to the invention. The internal electrode may contain Ni or a Ni alloy as the conductive material.

Using the present invention, it is possible to reduce the inconsistency of the sintering shrinkage between the internal electrode layer and the dielectric layer by uniformly sintering the BaTiO 3 dielectric slurry at a low temperature of 1100 ° C. or lower. Accordingly, the short rate can be reduced by suppressing the aggregation of the Ni internal electrodes. In addition, a multilayer ceramic capacitor that satisfies the X5R dielectric property can be obtained.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The invention, the alkali borosilicate (alkali-borosilicate) based glass that while having a low liquid phase forming temperature not higher than 1000 ℃ at the same time noting the experimental fact that a higher solubility of the BaTiO 3, the low temperature sintering of less than 1100 ℃ for BaTiO 3 The possibility as a preparation was confirmed. According to the glass composition of the present invention, by adding an appropriate amount of alkaline earth oxide (at least one of CaO and BaO) to an alkali borosilicate-based glass composition containing an appropriate alkali oxide, the capacitance temperature coefficient (Tcc) of the multilayer ceramic capacitor Can be stabilized to satisfy the X5R dielectric properties.

<Glass composition>

The glass composition of the present invention comprises lithium oxide (Li 2 O), potassium oxide (K 2 O), boron oxide (B 2 O 3 ) and silicon oxide (SiO 2 ), if necessary calcium oxide (CaO) and It may include one or more of barium oxide (BaO).

The SiO 2 content in the glass composition is 50 to 80 mol% based on the total moles of 100 of Li 2 O, K 2 O, CaO, BaO, B 2 O 3 and SiO 2 . Preferably, the content of SiO 2 is 55 to 75 mol%, more preferably 60 to 75 mol%. SiO 2 has a structure in which silicon atoms are bonded to four adjacent silicon atoms with four oxygen atoms surrounding them. Such SiO 2 is a glass network-former, which is the most important factor in determining the high temperature flowability, melting point, and solubility of BaTiO 3 matrix. When the SiO 2 content in the glass composition is less than 50 mol%, the solubility in the BaTiO 3 base material is poor and low temperature sinterability cannot be improved. When the SiO 2 content exceeds 80 mol%, the glass composition may be unsuitable as a sintering aid for low temperature sintering at 1100 ° C. or less because of high hot fluidity and a high liquidus formation temperature.

The content of B 2 O 3 in the glass composition is 5-20 mol%. B 2 O 3, together with SiO 2 , acts as a glass mesh forming oxide and is a major determinant of solubility in BaTiO 3 substrates. In addition, B 2 O 3 as a flux significantly lowers the melting point of the glass and serves to greatly improve the high temperature fluidity. In particular, in order to improve high temperature fluidity, B 2 O 3 is preferably added in a content of 5 mol% or more in the glass composition. When the content of B 2 O 3 exceeds 20 mol%, the chemical durability is liable to be lowered due to the weakening of the structure of the glass, and there is a concern that the glass forming ability is lowered due to crystallization.

The content of Li 2 O in the glass composition is 2-10 mol%. Li 2 O is a glass network-modifier (glass network-modifier), breaks the glass mesh structure consisting of SiO 2 or B 2 O 3 to lower the glass melting point, and serves to improve high temperature fluidity. When the content of Li 2 O is less than 2 mol%, the high temperature fluidity of the glass is lowered, and the liquidus formation temperature may be excessively high. When the content of Li 2 O exceeds 10 mol%, glass formation may be difficult due to the weakening and crystallization of the glass.

The content of K 2 O in the glass composition is 2-10 mol%. K 2 O, like Li 2 O, is a glass mesh modified oxide, which breaks the glass mesh structure composed of SiO 2 or B 2 O 3 to lower the glass melting point and serves to improve high temperature fluidity. In particular, when added simultaneously with other alkali oxides such as Li 2 O, K 2 O has a chemically complementary effect (mixed alkali effect), which not only enhances the chemical durability of the glass but also reduces the dielectric loss of the dielectric. Play a role. When the content of K 2 O is 2 to 10 mol%, the glass has an appropriate high temperature fluidity and an adequate complementary effect with Li 2 O can be obtained.

The content of CaO and BaO in the glass composition is 0-25 mol%. CaO is a mesh-modified oxide that reduces the melting point of the glass and at the same time serves to enhance the chemical durability by strengthening the structure of the glass weakened by alkali metal oxide. However, CaO has a disadvantage in that the high temperature viscosity of the glass is sharply lowered to cause rapid sintering shrinkage of the ceramic. BaO is a component capable of significantly lowering the melting point of glass among alkaline earth oxides, and in particular, serves to prevent rapid sintering shrinkage of the ceramic by smoothing the high temperature viscosity change of the glass. In addition, CaO and BaO serves to stabilize the capacity-temperature characteristics of the BaTiO 3 dielectric, if the addition amount is excessive, the sinterability is reduced. When the content of at least one of CaO and BaO exceeds 25 mol%, not only the glass forming ability is lowered, but also the low temperature sinterability of the BaTiO 3 dielectric is greatly weakened.

<Glass frit>

The glass frit of the present invention is composed of the glass composition according to the present invention, and is composed of a powder in an ultrafine spherical form having a particle size of 100 to 300 nm. In order to form a dielectric thin layer having a thickness of 3 μm or less, the BaTiO 3 base material used in the dielectric slurry has a particle size of about 150 to 300 nm, and subcomponents other than the sintering aid also have a particle size of several hundred nm or less. Therefore, when the particle size of the glass frit added to the dielectric slurry is 1 μm or more, it is difficult to uniformly sinter the dielectric thin layer having a thickness of 2-3 μm. In addition, when the shape of the glass frit is acicular or bulky, there is a possibility of causing uneven sintering, and it is advantageous to use a spherical glass frit. The glass frit of the present invention can be obtained by, for example, mechanically pulverizing a glass flake made of the glass composition and then performing a gas phase heat treatment.

Hereinafter, the manufacturing method of the glass frit of this invention is demonstrated. Here, the present invention will be described with reference to specific examples, but the present invention is not limited thereto.

First, the component powders (Li 2 O, K 2 O, CaO, BaO, B 2 O 3 and SiO 2 powders) are weighed and sufficiently mixed to satisfy the composition of the glass composition described above, followed by melting at 1400-1500 ° C. do. The glass flakes are then obtained by quenching through a twin roller and dry pulverized with a ball mill. By vapor-phase heat-treating the crushed glass, a glass frit in the form of ultra fine spherical powder having a particle size of 100 to 300 nm can be obtained.

The glass frit thus obtained is made of the glass composition described above, and may be used as a sintering aid for low temperature sintering of a multilayer ceramic capacitor. By using the glass frit made of the glass composition described above as a sintering aid, the BaTiO 3 dielectric layer can be uniformly sintered at a low temperature of 1100 ° C or less.

<Dielectric Composition>

The dielectric composition of the present invention is selected from the group consisting of BaTiO 3 as the main component, the glass composition described above as a minor component, MgCO 3 , rare earth oxides (Y 2 O 3 , Ho 2 O 3 , Dy 2 O 3, and Yb 2 O 3) . At least one species selected), and MnO. The content of the minor components is 1.0 to 3.0 mol of the glass composition, 0.5 to 2.0 mol of the MgCO 3 , 0.3 to 1.0 mol of the rare earth oxide and 0.05 to 1.0 mol of MnO based on 100 mol of the main component (BaTiO 3 ). .

By manufacturing a multilayer ceramic capacitor using a dielectric composition having such components and contents, low temperature sintering of 1100 ° C. or less can be realized and temperature stability of a capacity satisfying X5R dielectric characteristics can be obtained.

<Laminated Ceramic Capacitor>

1 is a cross-sectional view showing a multilayer ceramic capacitor according to an embodiment of the present invention. Referring to FIG. 1, the multilayer ceramic capacitor 100 includes a capacitor body 110 having a structure in which dielectric layers 102 and internal electrode layers 101 and 103 are alternately stacked. External electrodes 104 and 105 are formed on the outer surface of the condenser main body 110, and the external electrodes 104 and 105 are electrically connected to the corresponding internal electrodes 103 and 101, respectively.

The dielectric layer 102 includes the dielectric composition of the present invention described above. That is, the dielectric composition forming the dielectric layer 102, includes a sub ingredient containing a main component of BaTiO 3, and the above-mentioned glass composition. The auxiliary component is, relative to the main component as 100 mol, the glass composition includes 1.0 to 3.0 mol, MgCO 3 0.5 ~ 2.0 mol, the rare earth oxides 0.3 to 1.0 mol of MnO and 0.05 ~ 1.0 mol.

The thickness of the dielectric layer 102 is not particularly limited, but may be 3 μm or less per layer to implement an ultra-thin high capacity capacitor. Desirably, dielectric layer 102 may have a thickness of 1 to 3 μm. The conductive material contained in the internal electrodes 101 and 103 is not particularly limited. However, since the dielectric layer 102 has reduction resistance, it is preferable to use Ni or a Ni alloy as the material of the internal electrodes 101 and 103. Cu or Ni may be used as the material of the external electrodes 104.105.

Like the conventional multilayer ceramic capacitor, the multilayer ceramic capacitor 100 may be manufactured through a process of preparing a slurry, forming a green sheet, printing an internal electrode, laminating, pressing, and sintering.

Hereinafter, with reference to FIG. 2, the manufacturing process of the multilayer ceramic capacitor which concerns on one Embodiment of this invention is demonstrated concretely. First, the main component BaTiO 3 powder and the subcomponent powder are weighed and prepared so as to satisfy the above-described glass composition and dielectric composition (steps S1 and S1 '). That is, aLi 2 O-bK 2 O-cCaO-dBaO-eB 2 O 3 -fSiO 2 (a + b + c + d + e + f = 100, 2 ≦ in mol% based on 100 mol of BaTiO 3 as a main component glass made of ultra-fine spherical powder of 100-300 nm, composed of a≤10, 2≤b≤10, 0≤c≤25, 0≤d≤25, 5≤e≤20, 50≤f≤80 1.0 to 3.0 mol, MgCO 3 0.5 to 2.0 mol, rare earth oxide (at least one of Y 2 O 3 , Ho 2 O 3 , Dy 2 O 3 and Yb 2 O 3 ) 0.3 ~ 1.0 mol and MnO 0.05-1.0 mol are weighed.

Thereafter, the weighed powders are mixed and dispersed in an organic solvent (step S2), and the organic binder is further mixed to obtain a dielectric slurry (step S3). Polyvinyl butyral may be used as the organic binder, and acetone or toluene may be used as the solvent.

Thereafter, the slurry is molded into a sheet (green sheet) form (step S4). For example, the slurry may be molded into a green sheet having a thickness of 3 μm or less. Then, an internal electrode such as Ni is printed on the molded green sheet, and a plurality of green sheets on which the internal electrode is printed are laminated (step S5). Next, this laminate is compressed and cut into individual chips (green chips) (step S6). Next, the green chip is heated to a temperature of 250 to 350 ° C. to remove a binder, a dispersant, or the like in the chip.

Thereafter, the debindered laminate is sintered (fired), for example, at a temperature of 1100 ° C or lower (step S8). At this time, when the firing temperature of the firing exceeds 1150 ° C, peeling may occur between the dielectric layer and the internal electrode or the Ni electrode layer may aggregate as in the prior art. This is directly connected to the occurrence of a short circuit of the internal electrode and thus acts as a problem of lowering the reliability, it is preferable in the present invention to limit the firing temperature to 1100 ℃ or less.

Thereafter, an external electrode paste such as Cu or Ni is coated on the outer surface of the sintered body, and the paste is baked to form an external electrode (step S9). If necessary, to form a coating layer by plating on the outer electrode surface (step S10). Accordingly, a multilayer ceramic capacitor 100 as shown in FIG. 1 is obtained. Thereafter, various physical properties of the multilayer ceramic capacitor may be measured to evaluate the characteristics of the capacitor (step S11).

Through various experiments, the inventors have experimentally found that the multilayer ceramic capacitor using the glass composition and the dielectric composition satisfies X5R characteristics and exhibits excellent electrical characteristics.

<Example>

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to these examples. In the embodiment of the present invention, prior to fabrication of a commercially stacked chip, low-laminate specimens stacked about 10 layers were first manufactured to observe various physical properties.

The aLi 2 O-bK 2 O-cCaO-dBaO-eB 2 O 3 -fSiO 2 (a + b + c + d + e + f = 100, 2 ≦ a ≦ 10, 2 ≦ b ≦ 10, 0 ≦ c ≤25, 0≤d≤25, 5≤e≤20, 50≤f≤80), each element is weighed and sufficiently mixed to satisfy the composition shown in Table 1, and then mixed at 1400-1500 ° C. Melted. After quenching through a twin roller (twin roller) to obtain a glass flake (glass flake) and dry pulverized it by vapor-phase heat treatment to prepare an ultra-fine spherical powder glass frit having a particle size of 100 ~ 300nm. In addition, as a comparative material was prepared a glass frit that does not contain an alkali oxide (Li 2 O, K 2 O, etc.).

Figure 112005041868893-pat00001

Then, each subcomponent including the above glass frit was weighed as shown in Table 2, and then mixed and dispersed with an organic solvent.

Figure 112005041868893-pat00002

Thereafter, an organic binder was added and mixed to prepare a slurry, which was coated on the film at about 5 μm to prepare a molded sheet. Subsequently, Ni internal electrodes were printed, and each dielectric sheet on which the internal electrodes were printed was laminated 10 layers, and the upper and lower parts were further laminated with a molded sheet having no internal electrodes printed thereon. The laminate was cut at 15 ° C. under a pressure of 1000 kg / cm 2 for 15 minutes, and then cut to prepare a specimen. The specimens were heat-treated at 250 to 350 ° C. for 40 hours or more to incinerate organic binders and dispersants, and sintered at various temperatures within a range of 1050 to 1200 ° C. using a kiln with temperature and atmosphere control. At this time, the oxygen partial pressure in the firing atmosphere was controlled to 10 −11 to 10 −12 atmospheres. After the sintered specimens were coated with a Cu external electrode, electrode firing was performed at 850 to 920 ° C., and after the electrode firing was completed, a plating process was performed to complete the specimen production. The electrical characteristics were measured after a predetermined time using the prepared specimen.

The electrical characteristics of the specimens were measured at 1 KHz and 1 Vrms using a capacitance meter (Agilent, 4278A) and dielectric loss at 180 sec under rated voltage using a high resistance meter (Agilent, 4339B). Measured. In addition, the temperature dependence of the dielectric constant was measured by the change value from -55 ℃ to 135 ℃ using a TCC (Temperature characteristics coefficient) measuring equipment (4220A test chamber). The dielectric constant of each dielectric material at each firing temperature was calculated by calculating the dielectric layer thickness after firing. On the other hand, in the high temperature load test, a DC voltage of 18.9 V was applied at 150 ° C. and measured with the change over time of insulation resistance. The measurement results are shown in Table 3 below.

Figure 112005041868893-pat00003

As can be seen in Table 3, Inventive Examples 2 to 10 according to the present invention showed excellent sinterability at low temperature below 1100 ℃. In particular, in Examples 3 to 9, the dielectric constant and the specific resistance were excellent, and the temperature change rate (TCC) of the capacity was very stable. Accordingly, even when the samples of Inventive Examples 2 to 10 are fabricated with 400 laminated layers or more, it is expected that the X5R characteristics (-55 to 85 ° C., ΔC = ± 15% or less) are sufficiently satisfied. However, in contrast to the example of the present invention, the specimens of Comparative Examples 1 and 2 using BaO-CaO-SiO 2 based glass frit or BaSiO 3 based powder showed low sinterability at 1150 ° C. or lower, and sintering at 1100 ° C. or lower. It can be seen that it is not suitable at all.

It is intended that the invention not be limited by the foregoing embodiments and the accompanying drawings, but rather by the claims appended hereto. In addition, it will be apparent to those skilled in the art that the present invention may be substituted, modified, and changed in various forms without departing from the technical spirit of the present invention described in the claims.

As described above, by using the glass frit of the present invention, the BaTiO 3 dielectric layer is uniformly sintered at a low temperature of 1100 ° C. or lower, thereby reducing the sintering shrinkage mismatch between the internal electrode layer and the dielectric layer, and minimizing the aggregation of Ni to minimize the short circuit occurrence rate. In addition, it is possible to obtain a multilayer ceramic capacitor that can satisfy X5R dielectric properties (EIA standard: -55 ~ 85 ℃, △ C = ± 15%) as well as excellent electrical characteristics.

Claims (13)

  1. aLi 2 O-bK 2 O-cCaO-dBaO-eB 2 O 3 -fSiO 2 , wherein a, b, c, d, e and f are a + b + c + d + e + f = 100, 2≤a≤10, 2≤b≤10, 0≤c≤25, 0≤d≤25, 5≤e≤20, and 50≤f≤80.
  2. The method of claim 1,
    A, b, c, d, e and f satisfy 3≤a≤8, 2≤b≤5, 0≤c≤15, 0≤d≤15, 10≤e≤20, 55≤f≤75 A glass composition, characterized in that.
  3. The method of claim 1,
    A, b, c, d, e and f satisfy 3≤a≤8, 2≤b≤5, 0≤c≤15, 5≤d≤15, 12.5≤e≤17.5, and 60≤f≤75 A glass composition, characterized in that.
  4. Composition aLi 2 O-bK 2 O-cCaO-dBaO-eB 2 O 3 -fSiO 2 (a + b + c + d + e + f = 100, 2≤a≤10, 2≤b≤10, 0≤c ≤ 25, 0 ≤ d ≤ 25, 5 ≤ e ≤ 20 and 50 ≤ f ≤ 80,
    A glass frit characterized by being in the form of ultra-fine spherical powder having a particle size of 100 to 300 nm.
  5. The method of claim 4, wherein
    A, b, c, d, e and f satisfy 3≤a≤8, 2≤b≤5, 0≤c≤15, 0≤d≤15, 10≤e≤20, 55≤f≤75 Glass frit characterized in that.
  6. The method of claim 4, wherein
    A, b, c, d, e and f satisfy 3≤a≤8, 2≤b≤5, 0≤c≤15, 5≤d≤15, 12.5≤e≤17.5, and 60≤f≤75 Glass frit characterized in that.
  7. BaTiO 3 which is a main component;
    Composition aLi 2 O-bK 2 O-cCaO-dBaO-eB 2 O 3 -fSiO 2 (a + b + c + d + e + f = 100, 2≤a≤10, 2≤b≤10, 0≤c A subcomponent containing a glass composition represented by ≤ 25, 0 ≤ d ≤ 25, 5 ≤ e ≤ 20 and 50 ≤ f ≤ 80,
    The auxiliary component is, relative to the main component as 100 mol, the glass composition of 1.0 to 3.0 mol, MgCO 3 0.5 ~ 2.0 mol, rare earth oxide (the rare earth oxide is Y 2 O 3, Ho 2 O 3, Dy 2 O 3 and Yb 2 At least one selected from the group consisting of O 3 ) and 0.3 to 1.0 mole and 0.05 to 1.0 mole MnO.
  8. The method of claim 7, wherein
    A, b, c, d, e and f satisfy 3≤a≤8, 2≤b≤5, 0≤c≤15, 0≤d≤15, 10≤e≤20, 55≤f≤75 Dielectric composition, characterized in that.
  9. The method of claim 7, wherein
    A, b, c, d, e and f satisfy 3≤a≤8, 2≤b≤5, 0≤c≤15, 5≤d≤15, 12.5≤e≤17.5, and 60≤f≤75 Dielectric composition, characterized in that.
  10. A multilayer ceramic capacitor comprising a plurality of dielectric layers, a plurality of internal electrodes formed between the dielectric layers, and external electrodes electrically connected to the internal electrodes,
    The dielectric layer may include BaTiO 3 as a main component; Composition aLi 2 O-bK 2 O-cCaO-dBaO-eB 2 O 3 -fSiO 2 (a + b + c + d + e + f = 100, 2≤a≤10, 2≤b≤10, 0≤c A subcomponent containing a glass composition represented by ≤ 25, 0 ≤ d ≤ 25, 5 ≤ e ≤ 20 and 50 ≤ f ≤ 80,
    The auxiliary component is, relative to the main component as 100 mol, the glass composition of 1.0 to 3.0 mol, MgCO 3 0.5 ~ 2.0 mol, rare earth oxide (the rare earth oxide is Y 2 O 3, Ho 2 O 3, Dy 2 O 3 and Yb 2 At least one selected from the group consisting of O 3 ) A multilayer ceramic capacitor comprising 0.3 to 1.0 mol and 0.05 to 1.0 mol MnO.
  11. The method of claim 10,
    A, b, c, d, e and f satisfy 3≤a≤8, 2≤b≤5, 0≤c≤15, 0≤d≤15, 10≤e≤20, 55≤f≤75 Multilayer ceramic capacitor, characterized in that.
  12. The method of claim 10,
    A, b, c, d, e and f satisfy 3≤a≤8, 2≤b≤5, 0≤c≤15, 5≤d≤15, 12.5≤e≤17.5, and 60≤f≤75 Multilayer ceramic capacitor, characterized in that.
  13. The method of claim 10,
    Wherein said internal electrode contains Ni or a Ni alloy as a conductive material.
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